JPH0320438B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a lubricant additive containing sulfur, phosphorus and molybdenum. Sulfur-containing molybdenum salts of phosphorus-containing acids and methods for their production are disclosed in U.S. Pat.
No. 3256184, No. 3400140, No. 3494866, No.
No. 3840463 and No. 4156099. The main object of this invention is to provide a new composition containing sulfur, phosphorus and molybdenum prepared from a phosphorus-containing acid, and a method for its preparation. Another object is to provide new compositions containing sulfur, phosphorus and molybdenum made from phosphorus-containing acids and having reduced active sulfur. Yet another object is to provide novel compositions containing sulfur, phosphorous, and molybdenum that have friction-reducing properties in lubricants made from phosphorous-containing acids. Furthermore, it is an object of this invention to provide new concentrates containing these new sulfur, phosphorus and molybdenum containing compositions. Yet another object is to provide lubricant compositions containing novel compositions containing sulfur, phosphorus and molybdenum that reduce these frictions. Furthermore, it is an object of this invention to
The present invention provides a new method for reducing the fuel consumption of internal combustion engines by lubricating them with compositions containing sulfur, phosphorus and molybdenum that reduce friction. These and other objects of the invention are to obtain an olefinically unsaturated compound capable of reacting with active sulfur by reacting the following (a), (b) and (c) in the presence of (d). This is accomplished by providing a method for producing a composition comprising reacting the composition with a composition that is (a) A phosphorus-containing acid represented by the following formula: However, X and X' are each independently oxygen or sulfur, n is 0 or 1, and each R is independently the same or different hydrocarbon group. (b) at least one oxidized compound of hexavalent molybdenum; (c) Hydrogen sulfide. (d) Polar solvents. Typical phosphorus-containing acids (a) from which compositions of this invention are made are known. Examples of preferred phosphorus and sulfur containing acids are as follows. 1 Dihydrocarbylphosphinodithioic acid. For example, amylphosphinodithioic acid represented by the following formula. 2 S-Hydrocarbyl hydrogen hydrocarbyl phosphonotrithioate. For example, S expressed by the following formula
-Amylhydrogen amylphosphonotrithioate. 3 O-hydrocarbyl hydrogen hydrocarbyl phosphonodithioate. For example, O-
Amyl hydrogen amylphosphonodithioate. 4 S,S-dihydrocarbyl hydrogen phosphorotetrathioate. For example, diamyl hydrogen phosphorotetrathioate represented by the following formula. 5 O,S-dihydrocarbyl hydrogen phosphorotrithioate. For example, O,S-diamyl hydrogen phosphorotrithioate represented by the following formula. 6 O,O-dihydrocarbyl hydrogen phosphorodithioate. For example, O,O-diamylhydrogen phosphorodithioate represented by the following formula. [

The preferred acid represented by the formula can be easily obtained by reacting phosphorus pentasulfide (P ₂ S ₅ ) with an alcohol or phenol. This reaction takes place at temperatures ranging from about 20°C to about 200°C.
The process involves mixing 4 moles of alcohol or phenol with 1 mole of phosphorus pentasulfide at a temperature of . This reaction liberates hydrogen sulfide. Oxygen-containing analogs of these acids are easily obtained by treating dithioacids with water or steam;
This treatment replaces one or both sulfur atoms with oxygen atoms. Thus, as previously stated, preferred phosphorus containing acids are phosphorus and sulfur containing acids. These preferred acids are further preferably such that in the above formula, at least one X is sulfur, more preferably both X's are sulfur, at least one X' is oxygen or sulfur, and more preferably both X's are oxygen and n is 1. Mixtures of these acids may also be used in this invention. The term "hydrocarbon group" as used in this specification refers to a substantially saturated monovalent group derived from a hydrocarbon by removing one hydrogen from a carbon atom of the hydrocarbon. used for pointing. This carbon atom is directly bonded to the rest of the molecule. These hydrocarbon groups include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons,
Derived from mixed aliphatic-alicyclic hydrocarbons, mixed aliphatic-aromatic hydrocarbons, and mixed alicyclic-aromatic hydrocarbons. Therefore, these hydrocarbon groups can be called aliphatic groups, alicyclic groups, and the like. The hydrocarbons from which these groups are derived may contain non-reactive or substantially non-reactive polar or non-hydrocarbon substituents. In this specification, the term "substantially saturated" refers to acetylenically unsaturated (-C≡C-)
is intended to define a group in which no more than one ethylenically unsaturated bond (-C=C-) is included in the 10 covalent bonds between carbon atoms. Regarding the term "substantially saturated", the so-called double bonds in aromatic rings (e.g. benzene)
I don't think it contributes to unsaturation. Typically, as mentioned above, the substantially saturated monovalent group contains on average 1 or less ethylenic unsaturation. It is preferred that substantially all carbon-carbon bonds of the saturated group are saturated (with the exception of aromatic rings), ie, the group is free of acetylenic and ethylenically unsaturated bonds. Generally, the hydrocarbon group contains up to about 30 carbon atoms, with a preferred range of 1 to about 20 carbon atoms. The hydrocarbon group may contain non-reactive or substantially non-reactive polar or non-hydrocarbon substituents that do not substantially impair the reaction and the composition; It will be understood by those skilled in the art. Representative non-hydrocarbon or polar substituents include halogen substituents such as chlorine, fluorine, bromine and iodine, lower alkoxyl groups such as nitro, butoxy and hexyloxyl, pentylthio and heptylthio. groups such as lower alkylthio groups, hydroxyl groups, mercapto groups,

[Formula] Hido Localville, e.g.

[Formula] lower alkyl, h Dorocar Building

[Formula] includes hydrocarbons and other analogs. As a general rule, and particularly when the compositions of this invention are used as lubricant additives, the degree of substitution on the hydrocarbon group and the nature of the substituents will depend on the hydrocarbon nature of the group. It must not be something that damages the Thus, given this requirement, such groups usually contain no more than four substituents per group, and usually no more than one substituent per 10 carbon atoms in the group. be. Preferably, this hydrocarbon group is a pure hydrocarbyl (ie, a hydrocarbon group containing only carbon and hydrogen atoms). As in lower alkyl, the term "lower" as used herein to refer to groups is intended to indicate groups containing 7 or fewer carbon atoms. Preferred compositions of this invention include each R
are hydrocarbyl, especially, independently of each other, having up to about 30 carbon atoms, more preferably from 3 to about
Compositions made from 20 alkyl, aryl, alkaryl, and arylalkyl phosphorous acids are included. Preferred R is alkyl and alkaryl, more preferably alkyl. The hexavalent molybdenum oxide compound (b) useful in this invention is a water-soluble hexavalent molybdenum oxide compound that exhibits acidity in an aqueous solution. The chemistry of hexavalent molybdenum oxide compounds in aqueous solutions is well known to those skilled in the art and requires no further discussion. Acidic water-soluble hexavalent molybdenum compounds are obtained from compounds containing molybdenum trioxide or mixtures of two or more of these compounds. These compounds containing molybdenum trioxide include
Includes molybdenum trioxide (MoO ₃ ) and compounds made from molybdenum trioxide. Compounds containing molybdenum trioxide include MoO ₃ , molybdenum trioxide hydrate, molybdic acid, ammonium molybdate, alkali metal molybdates (e.g. sodium or potassium), and heteropolyarate salts of molybdate (e.g. phosphomolybdate). included. Preferred acidic water-soluble hexavalent molybdenum oxide compounds include molybdenum trioxide, molybdic acid, molybdic acid heteropolyacid salts, especially phosphomolybdates, alkali metal molybdates or ammonium molybdates, which are acidified with e.g. hydrochloric acid, acetic acid, sulfuric acid, etc. and those produced in an aqueous solution of MoO ₃ or its hydrate, in which the solubility of MoO ₃ or its hydrate is increased by adding an acid or a base. Also useful as (b) are MoOCl ₄ ,
There are hexavalent molybdenum oxyhalides such as MoO ₂ Cl ₂ , MoO ₂ Br ₂ , Mo ₂ O ₃ Cl ₆ and MoOF ₄ and mixtures thereof, which are hydrolyzed by water to form acidic water-soluble 6 It becomes a molybdenum oxide compound. A more detailed discussion of the properties of molybdenum trioxide compounds, in particular their descriptive matter, preparation, acidity and water solubility, can be found in "Molybdenum Compounds, Their Chemistry and Technology" by DHKilleffer and A. Linz.
(Molybdenum Compounds, Their Chemistry
and Technology) Interscience Publishers,
New York, 1952, Chapters 4, 6, 7, and 8 and ``Advanced Inorganic Chemistry Textbook'' by F.A. Cotton and G. Wilkinson.
Chemistry, A Comprehensive Text) 2nd
Edition, Interscience Publisher−Adivision of
John Wiley and Sons, New York, London,
Sidney, 1966, pages 930-960. Usually, the hexavalent molybdenum compound (b) or its precursor is dispersed or dissolved in the polar solvent (d). or,
(a) and (b) or their precursors are first mixed and then
(d) may be added. In some cases it may be desirable to generate (a) and/or (b) in situ, preferably in the presence of (d). For example, for (a), metal salts of acids containing phosphorus (e.g. alkali metal salts)
Acidification in the presence of (b) may produce (a). For example, for (b), by acidifying an alkali metal salt of molybdic acid in the presence of (a) and (d), the molybdenum trioxide-containing compound is converted into an acidic water-soluble
It can be used to generate the molybdenum compound (b) in situ. For the purposes of this invention, (a) and (b) must first be mixed, preferably in the presence of (d), before reaction with hydrogen sulfide (c). Hydrogen sulfide (c) is commercially available and can be fed into the reaction chamber either above or below the surface of the reaction mixture of (a) and (b) in the presence of (d). . Moreover, H ₂ S can also be generated and used on the spot. For example, alkali metal sulfides (e.g.
_H2S can be obtained by acidifying Na2S) with hydrochloric acid in the presence _of (a), (b) and (d). Polar solvents (d) useful in this invention include water,
and organic polar solvents such as alcohols, ethers, ketones, etc., and mixtures thereof. Preferred polar solvents (d) are water and mixtures of water and one or more organic polar solvents. Preferred organic polar solvents are lower alkyl alcohols, ethers and ketones. In addition to polar solvents, the reaction can be carried out in the presence of an essentially inert liquid solvent diluent.
The solvent diluent desirably serves to provide sustained contact of the reactants and to facilitate control of the reaction temperature. Suitable solvent diluent practices include aromatic and aliphatic hydrocarbons such as benzene, toluene, naphtha, mineral oil, hexane, etc., and chlorinated hydrocarbons such as dichlorobenzene, heptane chloride, and the like. In this specification, the term "essentially inert" when used in reference to solvent diluents, etc. means that the composition is resistant to chemical or physical changes under the conditions under which the solvent diluent, etc. is used. Used to mean sufficiently inert to not substantially impair the production, storage, mixing, and/or function of substances, additives, compounds, etc. For example, a small amount of a solvent diluent or the like may react or decompose only slightly without interfering with the production of the materials and use of the invention. In other words, such reactions or decompositions, if technically discernible, are not to the extent that they would deter a person skilled in the art from practicing the invention. The meaning of the term "essentially inert" as used herein will thus be readily understood by those skilled in the art. In this specification, "solvent diluent" is intended to include solvent diluents in which the respective reactants can be dissolved or stably dispersed. In this specification, "capable of stably dispersing" means that the composition (e.g., a single compound, a mixture of two or more compounds, etc.) can withstand a given solvent dilution without losing its intended function. It means that it can be dispersed in the agent. Thus, for example, if a composition is produced by reaction in an oil, the respective reactants can be suspended in the oil in a state capable of reacting to produce the composition. , is sufficient. Thus, the term "solvent diluent" will be understood and conventionally used by those skilled in the art. Although the products formed by reaction components (a), (b) and (c) in the presence of (d) can be used as lubricant additives, it is preferred to remove (d); This is especially true when water is water. (d) in the presence of
The compositions produced by the reactions of (a), (b) and (c) may sometimes be accompanied by by-products and/or excess solvent diluent, reducing commercial value. Accordingly, the polar solvent (d), undesirable by-products and/or excess undesirable solvent diluent can be further removed from the desired product by techniques known in the art, such as filtration, distillation (e.g. stripping), etc. can be separated from the compositions of this invention to obtain. Alternatively, if the solvent diluent is an oil suitable for use in the lubricant compositions of this invention, the product may remain in the solvent diluent and form the lubricant composition described below. You may use it to do so. Another problem that may reduce the commercial value of compositions produced by the reaction of (a), (b) and (c) in the presence of (d) is the It is sulfur that is active in This highly active sulfur is commonly referred to as corrosive or active sulfur. This active sulfur is highly reactive and corrosive to metals such as copper and silver. Therefore, reducing the active sulfur in the composition
This will reduce the corrosiveness of the composition to metals. Active sulfur is well known to those skilled in the art and requires no further discussion. The active sulfur contained in the compositions produced by the reaction of (a), (b) and (c) in the presence of (d) can make these compositions react with active sulfur.
Alternatively, it can be reduced by reacting with two or more olefinic unsaturated compounds. There are various naturally occurring olefinic unsaturated compounds that react with the active sulfur contained in the composition produced by the reaction of (a), (b), and (c) in the presence of (d). do. They contain at least one olefinic double bond, defined as a non-aromatic double bond, that is, a double bond connecting two aliphatic carbon atoms. In its broadest sense, olefins are defined by the formula R ₁ R ₂ C=CR ₃ R ₄ . Here, R ₁ , R ₂ , R ₃ and R ₄ are hydrogen or an organic group. In general, R other than hydrogen in the above formula can be satisfied if it is selected from the group shown below. -C( ^R5 ) ₃ , ^-COOR5 , -CON( ^R5 ) ₂ , -COON
( ^R5 ) ₄ , −COOM, −CN,

[Formula] R ⁵ , -X, -YR ⁵ , -Ar However, each R ⁵ is independently hydrogen,
It is alkyl, alkenyl, aryl, substituted alkyl, substituted alkenyl or substituted aryl, and any two R ⁵ can be alkylene or substituted alkylene forming a ring having up to 12 carbon atoms. M is one equivalent of a metal cation (preferably a Group or Group metal cation such as, for example, sodium, potassium, barium, calcium). X is halogen (eg chlorine, bromine, iodine). Y is oxygen or divalent sulfur. Ar is an aryl or substituted aryl group having 12 or less carbon atoms. Any two of R ₁ , R ₂ , R ₃ and R ₄ can also together form an alkylene or substituted alkylene group, ie, the olefinic compound can be an alicyclic compound. The nature of the substituents in the above-mentioned substituted moieties is not critical to this invention; any substituent may be used as long as it is compatible with the lubricating environment and does not cause any harm under the intended reaction conditions. As such, it is not intended to substitute compounds that are so unstable that they degrade and cause harm under the reaction conditions employed. However, substituents such as carbonyl groups, aldehyde groups, etc. are desirably sulfurized. Selection of appropriate substituents is easy for those skilled in the art or can be established by routine experimentation. Typical examples of such substituents include hydroxyl, amidine, amino,
Includes sulfonyl, sulfinyl, sulfonate, nitro group, phosphate, phosphite, mercapto alkali metal, and the like. The olefinically unsaturated compounds, when each R is not hydrogen, are usually, independently of each other, an alkyl, alkenyl or aryl, or (less frequently) a substituent thereof. Monoolefin and diolefin compounds are preferred, particularly the former, and further α-olefins, i.e. R ³ and R ⁴ are hydrogen and R ¹ and R ² are alkyl or aryl, especially alkyl (i.e. the olefin is aliphatic). Compounds in which case) are preferred. Olefinic compounds having about 8 to about 36 carbon atoms, particularly 8 to about 20 carbon atoms, are particularly preferred. Aliphatic alpha-olefins having from about 8 to about 36 carbon atoms are generally unbranched at carbon atoms having unsaturated double bonds. That is, the compound has CH ₂ =
Contains the part indicated by CH-. Further, these compounds are usually not branched even at the carbon atom at the 3-position. That is, the preferred olefin is CH ₂ =
Contains the part indicated by CHCH ₂ -. Preferred olefins contain about 8 to about 20 carbon atoms.
Mixtures of such olefins are commercially available and suitable for use in this invention. Furthermore, fatty acid esters derived from one or more unsaturated carboxylic acids are particularly useful as olefinic unsaturated compounds. The term "fatty acid" as used herein means an acid that can be obtained by hydrolyzing natural vegetable or animal fats or oils. These usually have about 16 to about 20 carbon atoms and include oleic acid, linoleic acid, and the like. Useful fatty acid esters are primarily those of fatty alcohols, including methanol,
Esters of monohydric alcohols such as ethanol, n-propanol, isopropanol, butanol, and ethylene glycol, propylene glycol,
Also included are esters of polyhydric alcohols such as trimethylene glycol, neopentyl glycol, and glycerin. Particularly preferred are fatty oils derived primarily from unsaturated fatty acids, ie naturally occurring triglycerides of higher carboxylic acids, especially linoleic acid and oleic acid. Such fatty oils include naturally occurring animal and vegetable fatty oils such as lard oil, peanut oil, cottonseed oil, soybean oil, and corn oil. The composition and properties of fatty oils are well known to those skilled in the art and are further described in Properties of the Principal, by MPDoss.
FATS, Fatty Oils, Waxes, Fatty Acids and
Their Salts) The Texas Company, 1952. A reaction mixture of (a) and (b) must first be prepared before the reaction with (c) in the presence of (d).
It is preferred that (d) is present when forming the reaction mixture of (a) and (b), especially before contacting (b) with (d).
It is preferable to disperse or dissolve it in The reaction mixture can be conveniently prepared at temperatures from about 0°C to about 150°C, preferably from about 25°C to about 100°C.
Produced at a temperature of ℃. The reactions of (a), (b) and (c) in the presence of (d) are conveniently carried out at temperatures of about 0°C to about 150°C. It is preferred, although not necessary, to maintain the temperature constant throughout the reaction. Adjust the reaction temperature from about 50℃ to about 100℃.
It is particularly preferable to adjust the temperature within the range of °C. The reaction of the composition formed by the reaction of (a), (b) and (c) in the presence of (d) with an olefinically unsaturated compound capable of reacting with active sulfur is carried out at a temperature of about 100°C.
from about 150°C, preferably from about 110°C to about 140°C
It is conveniently carried out at temperatures of °C. The time required for this reaction depends on various factors, such as the nature and amounts of the reactants, the reactor, the solvent diluent, and the degree of mixing. For the purposes of this invention, the molecular weight of a phosphorous acid (a) is equal to its equivalent weight, and therefore one mole of (a) is equal to its equivalent weight, and the equivalent weight is the acid value of the formula: is determined by assigning the respective values to . Equivalent weight = 56100 milligrams of KOH/equivalent/acid value (milligrams of KOH/gram) "Acid value" is the number of milligrams of KOH required to raise the pH of 1 gram of sample to approximately 4.0 in an aqueous solution. is defined as . The pH is about 4.0, which means it has a pH similar to that of bromophenol blue.
This can be confirmed by an indicator that changes color between 3.0 and 4.5, or by an electrical device such as a PH meter. In this invention, the ratio of reactants (a) and (b) is:
1 mol of molybdenum in (b) (for example, 1 mol of Na ₂ MoO ₄ contains 1 mol of molybdenum, ammonium paramolybdate (NH ₄ ) ₆ Mo ₇ O ₂₄ .
One mole of 4H ₂ O contains 7 moles of molybdenum. ), (a) is about 0.5 mol to about 4 mol. The proportion of hydrogen sulfide is at least about 0.5 per mole of molybdenum in the reaction mixture of (a) and (b).
Preferably in moles. Therefore, the ratio range of (a):(b):(c) is from about 0.5 moles to about 4.0 moles of (a): 1 mole of molybdenum in (b): at least 0.5 moles of _H2S ; Become. Excess hydrogen sulfide (i.e. (a):(b):(c) ratio of 1:1:>1.5) may be used to ensure completion of the reaction, but a ratio of 1:1:1.5 is acceptable. is optimal. A ratio of 1:1:4 or higher may be used, but to ensure completion of the reaction 1:1:
A ratio of 2 is sufficient. Excess hydrogen sulfide can be removed by bubbling an inert gas such as nitrogen through the reaction mixture. Preferred amounts of olefinically unsaturated compounds useful in this invention include (a), (b) and
This is the minimum amount necessary to react with all the active sulfur present in the composition produced by reaction (c). When 1.5 mol of hydrogen sulfide (c) is used per 1 mol of molybdenum in (b), the
It is believed that 0.5 moles of active sulfur are produced in reactions (a), (b) and (c). Also, 1 mole of olefinic double bond can react with 2 moles of active sulfur. Therefore, the required minimum amount of the olefinic unsaturated compound can be determined based on the stoichiometric relationship that 1 mole of olefinic double bond reacts with 2 moles of active sulfur formed. Although this ratio allows the reaction to be set stoichiometrically, the amount of olefinically unsaturated compound can be higher or lower than this ratio, depending on the circumstances. For example, a large amount (stoichiometric excess) of the olefinically unsaturated compound will usually be used to increase the reaction rate and ensure completion of the reaction with the active sulfur. Polar solvents (d) are essentially promoters or contact agents. Therefore, the minimum amount of polar solvent (d) is (a), (b) and
The amount necessary for the reaction (c) to proceed (i.e.
amount of hydrogen sulfide that reacts with (a) and (b) in the presence of (d))
It is. Generally, a sufficient amount of (d) as described above is used to disperse or preferably dissolve the molybdenum trioxide-containing compound or molybdenum oxyhalide compound. Generally, the polar solvent (d) is used in a weight ratio of about 1 to about 4 parts by weight per 1 part by weight of the above-mentioned molybdenum compound. Actually more than this
It is not uncommon for (d) to be used, but there is no benefit to it. Next, examples of this invention will be shown. Unless otherwise specified, all "parts" are parts by weight and all percentages are derived from parts by weight. Example 1 2035 parts (9.17 moles) of P ₂ S ₅ were added to 7335 parts (36.68 moles) of a commercially available alcohol having 12 to 14 carbon atoms at 80° C. under nitrogen to prepare a reaction mixture. _{P2S5 _}
was added over a period of 2 hours, during which time the temperature rose to 95°C due to the heat of reaction. The hydrogen sulfide produced was continuously removed and captured with caustic soda solution. The reaction mixture was air cooled for 2 hours with stirring under nitrogen.
The reaction mixture was filtered to obtain the desired O,O-dihydrocarbyl (C12-14) phosphorodithioic acid, and the acid number of the resulting acid was 96. Example 2 The same procedure as in Example 1 except that the C12 to C14 alcohol was replaced with an equimolar amount of 2-ethylhexyl alcohol to obtain the desired O,O-di-2-ethylhexylphosphorodithioic acid. repeated. The acid value of the obtained acid was 137. Example 3 584 parts (1
40 parts (1 mole) of sodium hydroxide, 190 parts of water and 144 parts (1 mole) of sodium hydroxide, prepared by heating a mixture of 500 parts of toluene and 500 parts of toluene until a clear solution is obtained.
of molybdenum trioxide at room temperature (26 °C). Then 100 parts (1 equivalent) of concentrated hydrochloric acid was added to the reaction mixture. The reaction mixture was heated at 40°C for 2 hours. 90 parts (2.6 moles) of hydrogen sulfide were added by spraying onto the surface of the reaction mixture for 3 hours. The temperature of the reaction mixture rose to 90° C. during the addition of hydrogen sulfide. The reaction mixture was then sparged with nitrogen to remove excess hydrogen sulfide and stripped under vacuum at 94°C.
O,O-dihydrocarbyl (12 to 14 carbon atoms)
the desired sulfur made from phosphorodithioic acid,
The reaction mixture was filtered to obtain a phosphorus and molybdenum containing composition. Example 4 3275 parts (8 mol) of O,O-di-2-ethylhexylphosphorodithioic acid prepared in Example 2,
A reaction mixture was made by adding to a room temperature suspension of 1152 parts (8.0 moles) of molybdenum trioxide in 2000 parts of water. The reaction mixture was heated to 80° C. and 533 parts of hydrogen sulfide was added by spraying onto the surface over a period of 6.5 hours. During this time, heat the reaction mixture at 80 to 90°C.
I kept it. The reaction mixture was sparged with nitrogen and stripped under vacuum at 95-100°C to remove excess hydrogen sulfide and to remove the desired sulfur, phosphorus, and A composition containing molybdenum was obtained. Example 5 360 parts (2.5 moles) of molybdenum trioxide, 24 parts of 85% phosphoric acid and 2000 parts of water were heated and boiled and reacted for 3 hours, then filtered through filter paper, and the residue was
A phosphomolybdic acid aqueous solution was prepared by washing with 150 parts of water. reducing the volume of the resulting solution;
921 parts of an aqueous solution containing 19.37% molybdenum were obtained. Example 6 To 1228 parts (3 moles) of O,O-di-2-ethylhexylphosphorodithioic acid prepared in Example 2, 1475 parts (3.0 parts) of phosphomolybdic acid prepared in Example 5 was added.
mol) was added dropwise over a period of 1 hour at room temperature. The reaction mixture was kept at 55°C for 3.5 hours. Next, hydrogen sulfide was blown into the reaction mixture from below the liquid surface while heating the reaction mixture under reflux. Hydrogen sulfide was bubbled in for 3 hours while the reaction mixture was maintained at 90-95°C. A total of 242 parts of hydrogen sulfide was added to the reaction mixture. The reaction mixture was then blown with nitrogen to remove excess hydrogen sulfide. 1000 parts of toluene were added to the reaction mixture and water was removed by azeotropic distillation. The reaction mixture was then filtered and stripped under vacuum at 95 DEG C. to yield the desired sulfur, phosphorus and molybdenum containing composition made from O,O-di-2-ethylhexylphosphorodithioic acid. Example 7 200 parts (5 moles) of sodium hydroxide, 1000 parts of water and 720 parts (5.0 moles) of molybdenum trioxide are heated to a clear solution, followed by 39 parts (0.25 moles) of 85% phosphoric acid. 2050 parts (5.0 mol) of O,O-2-ethylhexylphosphorodithioic acid prepared in Example 2 and 2500 parts
of toluene was added. After the addition was complete, 500 parts (5 moles) of concentrated hydrochloric acid was added to the reaction mixture.
Heated at 40°C for 2 hours. 318 parts (9.35 moles) of hydrogen sulfide were added to the reaction mixture from below the surface over a period of 10 hours. During the addition of hydrogen sulfide, the temperature of the reaction mixture rose to reflux. The reaction mixture was sparged with nitrogen and stripped under vacuum at 90°C to remove excess hydrogen sulfide. 2000 parts of toluene are added to the reaction mixture, which is filtered, stripped, and
A desired sulfur, phosphorus and molybdenum containing composition made from O-di-2-ethylhexylphosphorodithioic acid was obtained. Example 8 1152 parts (8 moles) of molybdenum trioxide, 77 parts (0.67 moles) of 85% phosphoric acid, 3000 parts of water and 3275 parts (8 moles) of O,O-di-
A mixture of 2-ethylhexylphosphorodithioic acids
Heated to 85°C. 533 parts of hydrogen sulfide was added to the reaction mixture from below the surface over 6.5 hours. The reaction mixture was kept at 80-90°C during the addition of hydrogen sulfide. Blow the reaction mixture with nitrogen and place under vacuum.
Excess hydrogen sulfide was removed by stripping at 95-100°C to yield the desired composition containing sulfur, phosphorus and molybdenum made from O,O-di-2-ethylhexylphosphorodithioic acid. Example 9 A reaction mixture of 4557 parts of the composition containing sulfur, phosphorus and molybdenum prepared in Example 4 and 1137 parts of a mixture of commercially available α-olefins having 15 to 18 carbon atoms was heated at 130°C for 3 hours. The reaction mixture was filtered to obtain the desired product. Example 10 Instead of α-olefin having 15 to 18 carbon atoms,
1139 parts commercial soybean oil and 681 parts commercial carbon number
The exact same procedure as Example 9 was repeated except that a mixture of 15 to 18 α-olefins was used. Example 11 The same procedure as in Example 10 was repeated, except that the same weight of the composition containing molybdenum obtained in Example 6 was used instead of the composition containing sulfur, phosphorus, and molybdenum. Example 12 446 parts of the composition containing sulfur, phosphorus and molybdenum obtained in Example 3, 73 parts of commercially available soybean oil and carbon number
The reaction mixture with 34 parts of a 15-18 α-olefin mixture was heated at 125-135°C for 6 hours. The reaction mixture was diluted with 2500 parts of toluene and filtered.
The filtrate was stripped to give the desired product. As previously mentioned, the compositions of this invention are also useful as additives in lubricants, in which they are primarily antioxidants, antiwear and/or extreme pressure agents and friction reducers. Work as. They can be used in a variety of lubricants based on oils of suitable viscosity as lubricants, including natural and synthetic lubricants and mixtures thereof. These lubricants include crankcase lubricants for spark-ignition and compression-ignition internal combustion engines, including automobile and truck engines, two-stroke engines, aircraft piston engines, marine and locomotive diesel engines, etc. . They are also used in gas engines, stationary power engines, turbines, etc. Automatic transmission fluids, transaxle lubricants, gear lubricants, metalworking lubricants, hydraulic fluids and other lubricating oil and grease compositions are also improved by the addition of the compositions of this invention. Natural oils include animal and vegetable oils (e.g. castor oil and lard oil) as well as liquid oils derived from petroleum and solvent-treated or acid-treated mineral oil lubricants based on paraffinic, naphthenic or mixtures thereof. It will be done.
Oils of suitable viscosity as lubricants derived from coal or shale are also useful oils. Synthetic lubricating oils include olefin polymers and copolymers (e.g. polybutylene, polypropylene, propylene-isobutylene copolymer, polybutylene chloride, poly(1-hexene), poly(1-octene), poly(1-decene)). and mixtures thereof), alkylbenzenes (e.g. dodecylbenzene, tetradodecylbenzene, dinonylbenzene, di(2-ethylhexyl)benzene, etc.), polyphenyl (e.g. biphenyl, terphenyl, alkyl polyphenyl, etc.), alkyl diphenyl ethers and alkyl Included are hydrocarbon oils and halogen-substituted hydrocarbon oils such as diphenyl sulfide and their derivatives, analogs and congeners. Polymers and copolymers of alkylene oxide and their derivatives, in which the terminal hydroxyl group is modified by esterification or etherification, form another group of synthetic lubricating oils. These include oils obtained by polymerization of ethylene oxide or propylene oxide, alkyl and aryl ethers of these polyoxyalkylene polymers (e.g. methyl-polyisopropylene glycol ether with an average molecular weight of 1000, polyethylene glycols with a molecular weight of 500 to 1000). diphenyl ether, diethyl ether of polypropylene glycol with a molecular weight of 1000 to 1500, etc.), monovalent or polyvalent carboxylic acid esters thereof (e.g. acetate ester, mixed fatty acid ester having 3 to 8 carbon atoms), or tetraethylene glycol having 13 carbon atoms It is typified by diesters of oxygen acids. Another group of suitable synthetic lubricating oils are dicarboxylic acids such as phthalic acid, succinic acid, alkylsuccinic acid and alkenylsuccinic acid, maleic acid, azelaic acid, suberic acid, sebacic acid, fumaric acid,
adipic acid, linoleic acid dimer, malonic acid, alkylmalonic acid, alkenylmalonic acid, etc.) and various alcohols (e.g. butyl alcohol, hexyl alcohol, dodecyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, diethylene glycol monoether, propylene) It consists of esters with glycols, etc.). Specific examples of these esters include dibutyl adipate, di(2-ethylhexyl) sebacate, diisooctyl azelate, di-n-hexyl fumarate,
Dioctyl sebacate, diisodecyl azelate, dioctyl phthalate, didecyl phthalate, dieicosyl sebacate, 2-linoleic acid doublet
Examples include ethylhexyl diester, a complex ester obtained by reacting 1 mol of sebacic acid with 2 mol of tetraethylene glycol and 2 mol of 2-ethylhexanoic acid. Esters useful as synthetic oils also include those derived from monocarboxylic acids and polyhydric alcohols having 5 to 12 carbon atoms and polyhydric alcohol ethers such as neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol. It also includes esters. Silicon-based oils, such as polyalkyl-, polyaryl-, polyalkoxy-, or polyaryloxy-siloxane oils and silicate oils, also form another group of useful synthetic lubricants (e.g. Tetraethyl acid, tetraisopropyl silicate,
Tetra-(2-ethylhexyl) silicate, tetra-(4-methyl-2-ethylhexyl) silicate, tetra-(p-tert-butylphenyl) silicate, hexa-(4-methyl-2-pentoxy)-disiloxane , poly(methyl)-siloxane, poly(methylphenyl)siloxane, etc.). Other synthetic lubricants include
Liquid esters of acids containing phosphorus (eg, tricresyl phosphate, trioctyl phosphate, diethyl ester of decylphosphonic acid, etc.), polymerized tetrahydrofuran, and the like are included. Unrefined, refined and rerefined oils (and mixtures thereof) of the types previously disclosed can be used in the lubricant compositions of this invention. Unrefined oils are oils obtained directly from natural or artificial sources without further refining treatment. For example, shale oils obtained directly from retorting operations, petroleum oils obtained directly from distillation, or esters obtained directly from an esterification process are unrefined oils when used without further treatment. In order to improve one or more properties of refined oil,
It is similar to unrefined oil except that it has undergone one or more further refining treatments. Many such purification techniques are known to those skilled in the art, such as solvent extraction, acid or base extraction, filtration, percolation, etc. Rerefined oil is obtained from already used refined oil by operations similar to those used to obtain refined oil. Rerefined oil, also known as reclaimed oil or reprocessed oil, is often further processed by operations to remove spent additives and oil breakdown products. Generally, the lubricants of the present invention include an amount of the present invention sufficient to improve properties such as oxidative stability and/or wear resistance and/or extreme pressure properties and/or friction reducing properties. The composition includes: Typically, this amount ranges from about 0.05% to about 20% of the total weight of the lubricant.
%. Preferably it is about 0.1% to about 10%, more preferably about 0.1% to about 5% and especially about 0.5% to about 2%. In lubricants used under extremely harsh conditions, such as marine diesel engine lubricants, the reaction products of this invention will amount to about 30% by weight. This invention also contemplates the use of other additives with the compositions of this invention. Such additives include, for example, auxiliary detergents and dispersants of the ash-forming or ashless type, corrosion and antioxidants, pour point depressants, extreme pressure additives, color stabilizers, anti-foaming agents, and the like. Ash-forming detergents are alkali metal or alkaline earth metal, sulfuric acid, carboxylic acid, or olefin polymers (e.g., 1000 molecular weight polyisobutene) combined with phosphorus trichloride, phosphorus heptasulfide, phosphorus pentasulfide, phosphorus trichloride and sulfur, yellow Lipid-soluble organic phosphoric acids, such as organic phosphoric acids characterized as having at least one bond in which carbon and phosphorus are directly bonded, obtained by treatment with phosphorus and sulfur halides, or phosphating agents such as phosphorothioyl chloride. It is represented by the neutral or basic salt of Among the salts of such acids, the most commonly used are the sodium, potassium, lithium, calcium, magnesium, strontium and barium salts. The term "basic salt" is used to refer to metal salts in which the metal is present in stoichiometrically greater abundance than the organic acid groups. A commonly used method for making basic salts involves using a solution of the acid in mineral oil with an excess of a metal neutralizing agent, such as a metal oxide, hydroxide, carbonate, bicarbonate or sulfide. One method is to heat it above 50℃ and filter it. It is known that the use of promoters in the neutralization step results in much higher metal uptake. Examples of compounds useful as accelerators include phenols,
Phenols such as naphthol, alkylphenol, thiophenol, sulfurized alkylphenol, and condensation products of phenols and formaldehyde, methanol, 2-propanol, octyl alcohol, cellosolve, carbitol, ethylene glycol, stearyl alcohol, and cyclohexyl alcohol and amines such as aniline, phenylenediamine, phenothiazine, phenyl-β-naphthylamine, and dodecylamine. A particularly effective method of making basic salts is to mix the acid with excess basic alkaline earth metal neutralizer and at least one alcohol promoter, for example at 60°C or 200°C.
It consists of carbonating this mixture at elevated temperature. Supplemental ashless detergents and dispersants are called ``ashless'' even though, depending on their structure, they produce non-volatile substances such as boron oxide and phosphorus pentoxide upon combustion. However, they are usually metal-free and therefore do not produce metal-containing ash when burned. Many of this type are known in the art, and any are suitable for use in the lubricants of this invention. Below is an example. (1) at least about 34, preferably at least about
carboxylic acids containing 54 carbon atoms (or their derivatives), nitrogen-containing compounds such as amines,
Reaction products with organic compounds with hydroxyl groups, such as phenols and alcohols, and/or basic inorganic compounds. These "carboxylic acid dispersants" are described in British Patent No. 1306529 and in a number of US patents listed below. 3163603
3351552 3541012 3184474 3381022 3542678
3215707 3399141 3542680 3219666 3415750
3567637 3271310 3433744 3574101 3272746
3444170 3576743 3281357 3448048 3630904
3306908 3448049 3632510 3311558 3451933
3632511 3316177 3454607 3697428 3340281
3467668 3725441 3341542 3501405 Re26433
3346493 3522179 (2) Reaction products of relatively high molecular weight aliphatic or cycloaliphatic halides and amines, preferably polyalkylene polyamines. These can be characterized as "amine dispersants" and are described, for example, in the following US patents: 3275554, 3454555, 3438757, 3565804 (3) Reaction products of alkylphenols having an alkyl group containing at least about 30 carbon atoms with aldehydes (especially formaldehyde) and amines (especially polyalkylene polyamines). This is characterized as a "Mannitzsch dispersant" and the materials described in the following US patents are examples of this. 3413347, 3725480, 3697574, 3726882,
3725277 (4) Carboxylic acid-based, amine or Mannitz dispersants with urea, thiourea, carbon disulfide, aldehyde,
Ketones, carboxylic acids, hydrocarbon-substituted succinic anhydrides, nitriles, epoxides, boron compounds,
Substances obtained by treatment with reagents such as phosphorus compounds.
Examples of materials of this type are described in the following US patents: 3036003 3282955 3493520 3639242 3087936
3312619 3502677 3649229 3200107 3366569
3513093 3649659 3216936 3367943 3533945
3658836 3254025 3373111 3539633 3697574
3256185 3403102 3573010 3702757 3278550
3442808 3579450 3703536 3280234 3455831
3591598 3704308 3281428 3455832 3600372
3708522 (5) Lipid-soluble monomers such as decyl methacrylate, vinyl decyl ether and large molecular weight olefins and polar substituents such as aminoalkyl acrylate or acrylamide and poly-(oxyethylene) substituted acrylates, etc. Copolymer with monomer containing. These can be characterized as "polymerizing dispersants" and examples of these are described in the following US patents: 3329658 3666730 3449250 3687849 3519565
3702300 Extreme pressure additives and corrosion and oxidation inhibitors are represented by the following: (1) Chlorinated aliphatic hydrocarbons such as chlorinated waxes. (2) Organic sulfides and polysulfides such as benzyl disulfide, bis(chlorobenzyl) disulfide, dibutyl tetrasulfide, sulfurized methyl ester of oleic acid, sulfurized alkylphenol, dipentene sulfide, and terpene sulfide. (3) Phosphorus sulfide hydrocarbons, such as the reaction products of phosphorus sulfide and turpentine or methyl oleate. (4) Dibutyl phosphite, diheptyl phosphite, dicyclohexyl phosphite, pentyl phenyl phosphite, dipentyl phosphite, tridecyl phosphite, distearyl phosphite, dimethylnaphthyl phosphite, phosphorous Phosphorus esters mainly containing dihydrocarbon and trihydrocarbon phosphites such as 4-pentylphenyl acid oleyl, polypropylene (molecular weight 500) substituted phenyl phosphite, diisobutyl substituted phenyl phosphite, etc. (5) Thiocarbamate metal salts such as zinc dioctylthiocarbamate and barium heptylphenyldithiocarbamate. (6) Zinc dicyclohexylphosphorodithioate, zinc dioctylphosphorodithioate, barium di(heptylphenyl)phosphorodithioate, cadmium dinonylphosphorodithioate, and a mixture of equimolar amounts of phosphorus pentasulfide, isopropyl alcohol, and n-hexyl alcohol. such as the zinc salt of phosphorodithioic acid produced by the reaction with
Group metal salts of phosphorodithioic acids. The compositions of this invention can be added directly to lubricants. However, to form a concentrate of additives, essentially inert materials such as mineral oil, naphtha, benzene, toluene, or xylene, etc.
Dilution with a normally liquid organic diluent is preferred. Such concentrates typically contain from about 20 to about 90% by weight of the compositions of this invention, and additionally contain 1 or 2% by weight of the compositions of this invention.
Other additives mentioned above may also be included. The lubricant composition produced according to this invention comprises:
1% by weight of mineral oil with a suitable viscosity as a lubricant
can be represented by the lubricant composition obtained by treatment with the product obtained in Example 9 of .

Claims (1)

[Claims] 1 (a) General formula (wherein, X and X' are each independently oxygen or sulfur, n is each 0 or 1, and R is each independently a hydrocarbon group having up to 30 carbon atoms); (b) at least one water-soluble hexavalent molybdenum oxide compound that is acidic in aqueous solution; molar ratio of c), (d)
A method for producing a lubricant additive, which comprises reacting at about 0 to 150°C in the presence of a polar solvent. 2. The manufacturing method according to claim 1, wherein the hydrocarbon group is an aliphatic group. 3. The method according to claim 2, wherein the aliphatic group is alkyl having 3 to about 30 carbon atoms. 4 At least one X is sulfur, at least one X' is oxygen, and each n is 1
The method according to claim 3, wherein: 5. A reaction mixture of (a) and (b) is first prepared in the presence of (d), and then this is mixed at a temperature between 0°C and 150°C.
(c) The method according to claim 4, wherein the method is reacted with (c). 6. The method of claim 5, wherein (d) is water, an organic polar solvent, or a mixture thereof. 7. Claim 1, wherein the hexavalent molybdenum oxide compound (b) is an acidic, water-soluble hexavalent molybdenum compound obtained from a molybdenum trioxide compound or a mixture of one or more of these compounds. the method of. 8. The method according to claim 7, wherein the molybdenum trioxide compound is molybdenum trioxide, molybdenum trioxide hydrate, molybdic acid, ammonium molybdate, alkali metal molybdate, or heteropolyacid salt of molybdate. 9. Claim 4, wherein the hexavalent molybdenum oxide compound (b) is an acidic water-soluble hexavalent molybdenum compound obtained from a molybdenum trioxide compound or a mixture of one or more of these compounds. the method of. 10 The molybdenum trioxide compound is molybdenum trioxide, molybdenum trioxide hydrate, molybdic acid,
10. The method according to claim 9, which is ammonium molybdate, alkali metal molybdate, or heteropolyacid molybdate. 11 The hexavalent molybdenum oxide compound (b) is an acidic water-soluble hexavalent molybdenum oxide compound obtained from a molybdenum trioxide compound or a mixture of one or more of these compounds.
7. The method according to claim 6, which is a monovalent molybdenum compound. 12 The molybdenum trioxide compound is molybdenum trioxide, molybdenum trioxide hydrate, molybdic acid,
12. The method according to claim 11, which is ammonium molybdate, alkali metal molybdate, or heteropolyacid molybdate. 13. The method according to claim 8, wherein the molybdate heteropolyacid salt is a phosphomolybdate. 14. The method according to claim 10, wherein the molybdate heteropolyacid salt is a phosphomolybdate salt. 15. The method according to claim 12, wherein the molybdate heteropolyacid salt is a phosphomolybdate. 16. The method of claim 1, wherein (d) is water. 17. The method of claim 4, wherein (d) is water. 18. The method of claim 6, wherein (d) is water. 19. The method of claim 8, wherein (d) is water. 20. The manufacturing method according to claim 10, wherein (d) is water. 21. The manufacturing method according to claim 12, wherein (d) is water. 22. The manufacturing method according to claim 15, wherein (d) is water.